WO2012106598A2 - High voltage battery for a lithium battery - Google Patents
High voltage battery for a lithium battery Download PDFInfo
- Publication number
- WO2012106598A2 WO2012106598A2 PCT/US2012/023774 US2012023774W WO2012106598A2 WO 2012106598 A2 WO2012106598 A2 WO 2012106598A2 US 2012023774 W US2012023774 W US 2012023774W WO 2012106598 A2 WO2012106598 A2 WO 2012106598A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrolyte
- solvent
- lithium
- lithium battery
- battery
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention provides an electrolyte solution, particularly useful for lithium batteries that includes succinonitrile and a co-solvent that has improved conductivity and, in turn, better battery performance.
- Lithium ion batteries have been in commercial use since 1991 and have been conventionally used as power sources for portable electronic devices. See, e.g., U.S.
- WO 2008/138132 Al to Abouimrane Ali et al describes the utility of dinitrile based liquid electrolytes and exemplifies SCN that can be combined with a co-solvent, such as propylene carbonate (see pages 5 and 6) in a ratio of 1 :99 to 99: 1. There is a specific example where the ratio is 1 : 1 (see page 7, legend to FIG. 4).
- Li BOB is suggested as an example of an ionic salt to be used in the liquid electrolyte (see page 6, lines 4-6).
- the amount of dinitrile is suggested to range from 10 to 90 % v/v with preferred ranges at 16-80 and 25-75% v/v (see page 5, lines 21 -23).
- U.S. 2008/0102369 to Sakata, Hideo et al describes a nonaqueous secondary battery that can include a lithium electrolyte salt (see page 2, paragraph [0025]) and a nitrile compound such as SCN in an amount of at least 0.005% by weight and suggest the maximum amount that should be include is 1% by weight (see page 3, paragraph [0029] and [0031 ]).
- This publication also suggests that the solvent can be and/or include propylene carbonate (see page 2, paragraph [0023]).
- U.S. 7,226,704 to Panitz, Jan-Christoph et al generally describes lithium salts such as LiBOB (see col. 2, line 47) with 35 to 55 wt% of carbonates such as propylene carbonate (see col. 2, lines 50-52 and col. 3, line 14) with dinitriles in an amount of 5 to 40wt% (see col. 2, lines 533-60 and col. 3, lines 53-54).
- lithium salts such as LiBOB (see col. 2, line 47) with 35 to 55 wt% of carbonates such as propylene carbonate (see col. 2, lines 50-52 and col. 3, line 14) with dinitriles in an amount of 5 to 40wt% (see col. 2, lines 533-60 and col. 3, lines 53-54).
- CA 2435218 Al to Abu-Lebdeh, Yaser et al describes a plastic crystal electrolyte that can include lithium salt and succinonitrile (see page 9, Example 1 ).
- the present invention is based on the surprising discovery that an electrolyte for a Li battery , particularly one using Li BOB as the ionic salt, , which comprises the combination of succinonitrile (SCN) and up to 40% (by weight) of propylene carbonate, by itself or in combination with additional secondary solvents yields improved conductivity thereby enhancing battery performance in terms of capacity, power and resistance.
- SCN succinonitrile
- propylene carbonate up to 40% (by weight) of propylene carbonate
- one embodiment of the present invention is an electrolyte, comprising a lithium salt and from 20 to 80 wt% succinonitrile and 5 to 40 wt% of at least one co-solvent.
- Another embodiment of the present invention is a rechargeable lithium battery, comprising an anode; a cathode; and an electrolyte; wherein the electrolyte comprises a lithium salt and from 20 to 80 wt% succinonitrile and 5 to 40 wt% of at least one co-solvent.
- FIG. 1 depicts log conductivity as a function of temperature for differing
- the electrolyte of the present invention includes a lithium salt, succinonitrile (as used herein defined as a solvent even though it is solid at room temperature) and at least one co- solvent, preferably propylene carbonate, by itself or in combination with other secondary or co-solvents.
- the purpose of the co-solvent is to improve the low-temperature performance of the SCN-based electrolyte, without reducing the voltage stability of the resulting electrolyte solution.
- an electrolyte solution with a voltage stability in excess of 5.5V would be maintained, while increasing the conductivity at room temperature and below to the milli- Siemens range.
- co-solvents may be organic, inorganic or a mixture thereof.
- the co-solvent may be, for example, dimethyl carbonate (DMC), diethyl carbonate (DEC), , ethylene carbonate (EC), methyl propyl carbonate (MPC), dimethyl formamide (DMF), tetrahydrofuran (THF), 2-methyl tetrahydrofuran, 2-chloromethyl tetrahydrofuran, methyl formate, methyl acetate, ⁇ -butyrolactone (BL or ⁇ -BL), acetonitrile (ACN), 3-methoxypropionitrile (MPN), tetramethylene sulfone ((CHj) 4 S0 2 ), dimethyl sulfoxide (DMSO), tetraethylsulfonamide (TESA), dimethyl sulfite, sulfolane (SL), 1 ,3- dioxolane, dime
- DMC dimethyl carbonate
- the co-solvent including propylene carbonate, individually or mixtures thereof, is present in an amount of 5 to 40 wt%, inclusive of from 5 to 20 wt%, 10 to 20 wt%, 15 to 20 wt% and all values and ranges there between, e.g., 7, 12, 16, 19, 25, 30, 32, 35, and 38.
- a mixture of co-solvents is used.
- its desirable to minimize the amount of co-solvent as these have lower voltage stability.
- the succinonitrile is present in the electrolyte in an amount of 20 to 80 wt%, inclusive of 30 to 60 wt% succinonitrile, 40 to 50 wt% succinonitrile, and all values and ranges there between, e.g., 25, 27, 32, 35, 38, 41 , 43, 45, 48, 52, 55, 59, 63, 65, 68, 70, 73, 75, 77 and 79.
- lithium bioxalato borate salt Li[C 2 0 4 ] 2 B
- lithium bis- trifluoromethanesulphonylimide Li(CF 3 S0 2 ) 2 N
- lithium bis- perfluoroethylsulphonylimide Li(C 2 F 5 S0 2 ) 2 N
- LiC 2 0 4 BF 2 lithium tetrafluoroborate
- LiPF 6 lithium hexafluorophosphate
- LiSCN lithium thiocyanate
- LiC 3 SO3 lithium triflate
- the lithium salt is lithium bioxalato borate.
- the lithium salt may be present in the electrolyte in any suitable amount, for example, in an amount of from 1-20 mol%, inclusive of all values and ranges there between, including 2, 4, 5, 7, 9, 12, 15, 17, and 19.
- the present invention also provides an electrochemical device, e.g., a rechargeable lithium battery that includes the electrolyte composition described herein.
- a rechargeable lithium battery that includes the electrolyte composition described herein.
- the battery includes, in addition to the electrolyte, an anode and a cathode.
- the anode in a LiB typically includes to form a solid electrolyte interface (SEI) in order to function in an LiB.
- SEI solid electrolyte interface
- LiB electrolytes contain a film forming additive to most effectively and efficiently form this film.
- the electrolyte of this invention may further include such an additive.
- the additive for forming a solid electrolyte interface film on the anode is present in amounts of about 0.2 to 5 wt%, including 0.5, 1 , 1.5, 2, 2.5, 3, 3.5, 4, 4.5 and all values and ranges there between.
- Non-limiting examples of the additive for forming a solid electrolyte interface film on the anode are vinylene carbonate, vinylethelene carbonate, LiPF 6 , LiBOB, and combinations thereof.
- the electrochemical device can be used in other devices such as rechargeable consumer electronics, automotive applications (e.g., gas-hybrid vehicles) and in other commercial applications where a rechargeable device is useful.
- the electrolyte was made by:
- the SCN is melted, by placing the SCN on a hot plate at a maximum set point of 70°C.
- the separator For proper wetting, the separator must be impregnated with the liquid electrolyte (in one example, when the co-solvent amount was low, the SCN mixture solidified at RT). This can be done by running the separator through the electrolyte and wicking off excess; or by adding a controlled amount of electrolyte (ex, using warm pipette) to the test cell.
- the liquid electrolyte in one example, when the co-solvent amount was low, the SCN mixture solidified at RT.
- An electrolyte was made by combining succinonitrile (SCN) and 20% of either propylene carbonate (PC) or ethyl methyl carbonate (EMC). To this 4 mol% of LiBOB was added and stirred until the LiBOB was completely dissolved.
- the electrolyte solution was tested for conductivity by adding the solution to the separator of a test cell (that included from bottom to top: a case, separator, SUS spacer, spring, gasket and cover). The electrodes were SUS/SUS. Impedance spectroscopy was used to measure resistance and subsequently calculate conductivity. Impedance spectra are measured at different temperatures to produce the test results shown in FIG. 1.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE112012000670T DE112012000670T5 (en) | 2011-02-04 | 2012-02-03 | High voltage battery for a lithium battery |
JP2013552675A JP2014516454A (en) | 2011-02-04 | 2012-02-03 | High voltage battery for lithium battery |
CN201280007668.8A CN103733412A (en) | 2011-02-04 | 2012-02-03 | High voltage battery for a lithium battery |
KR1020137023189A KR20140025343A (en) | 2011-02-04 | 2012-02-03 | High voltage battery for a lithium battery |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/020,854 | 2011-02-04 | ||
US13/020,854 US20120202121A1 (en) | 2011-02-04 | 2011-02-04 | High voltage battery for a lithium battery |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2012106598A2 true WO2012106598A2 (en) | 2012-08-09 |
WO2012106598A3 WO2012106598A3 (en) | 2014-03-20 |
Family
ID=46600830
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2012/023774 WO2012106598A2 (en) | 2011-02-04 | 2012-02-03 | High voltage battery for a lithium battery |
Country Status (6)
Country | Link |
---|---|
US (1) | US20120202121A1 (en) |
JP (1) | JP2014516454A (en) |
KR (1) | KR20140025343A (en) |
CN (1) | CN103733412A (en) |
DE (1) | DE112012000670T5 (en) |
WO (1) | WO2012106598A2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015083841A1 (en) * | 2013-12-03 | 2015-06-11 | University Of Massachusetts Amherst | Electrical insulation layer and battery device |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10804566B2 (en) | 2015-09-16 | 2020-10-13 | Umicore | Lithium battery containing cathode material and electrolyte additives for high voltage application |
KR20190116584A (en) * | 2015-09-16 | 2019-10-14 | 유미코아 | Lithium battery containing cathode material and electrolyte additives for high voltage application |
JP2019114390A (en) * | 2017-12-22 | 2019-07-11 | 日本ゼオン株式会社 | Electrolyte composition for electrochemical device and manufacturing method of electrode for electrochemical device |
CN109659608A (en) * | 2018-11-16 | 2019-04-19 | 湖北锂诺新能源科技有限公司 | A kind of preparation method and application of tetrafluoro lithium aluminate |
CN109638350B (en) * | 2018-12-18 | 2022-08-16 | 西北工业大学 | Lithium-stable solid electrolyte containing nitrile groups, preparation method and application thereof |
WO2022211404A1 (en) * | 2021-03-30 | 2022-10-06 | 주식회사 엘지에너지솔루션 | Lithium secondary battery and manufacturing method therefor |
Citations (5)
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US20070015048A1 (en) * | 2005-07-13 | 2007-01-18 | Hochun Lee | Lithium secondary battery containing capsule for controlled-release of additives |
US20090068562A1 (en) * | 2007-09-07 | 2009-03-12 | Kyoung-Han Yew | Rechargeable lithium battery |
US20090092902A1 (en) * | 2005-07-29 | 2009-04-09 | Ali Abouimrane | Plastic crystal electrolyte for lithium batteries |
US20100015521A1 (en) * | 2008-07-07 | 2010-01-21 | Jinhee Kim | Rechargeable battery and associated methods |
US20100119951A1 (en) * | 2007-05-11 | 2010-05-13 | Ali Abouimrane | Plastic Crystal Electrolyte with a Broad Potential Window |
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DE19829030C1 (en) | 1998-06-30 | 1999-10-07 | Metallgesellschaft Ag | Lithium bisoxalatoborate used as conducting salt in lithium ion batteries |
DE10111410C1 (en) | 2001-03-08 | 2002-07-25 | Chemetall Gmbh | Lithium bis(oxalato)borate electrolyte, used in electrochemical storage system or electrochromic formulation, e.g. window, contains ternary solvent system |
CN100585935C (en) | 2002-07-15 | 2010-01-27 | 宇部兴产株式会社 | Non-aqueous electrolyte and lithium cell |
CA2435218A1 (en) | 2003-07-28 | 2005-01-28 | Michel Armand | Plastic crystal electrolytes based on a polar, neutral matrix |
TWI306680B (en) | 2004-05-28 | 2009-02-21 | Lg Chemical Ltd | Additives for lithium secondary battery |
JP4936440B2 (en) | 2006-10-26 | 2012-05-23 | 日立マクセルエナジー株式会社 | Non-aqueous secondary battery |
KR100814885B1 (en) | 2006-11-17 | 2008-03-20 | 삼성에스디아이 주식회사 | Rechargeable lithium battery |
KR100814826B1 (en) | 2006-11-20 | 2008-03-20 | 삼성에스디아이 주식회사 | Rechargeable lithium battery |
KR100814827B1 (en) | 2007-04-05 | 2008-03-20 | 삼성에스디아이 주식회사 | Electrolyte for rechargeable lithium battery and rechargeable lithium battery |
WO2008138132A1 (en) * | 2007-05-15 | 2008-11-20 | National Research Council Of Cananda | Dinitrile-based liquid electrolytes |
JP5247196B2 (en) * | 2008-03-19 | 2013-07-24 | 三洋電機株式会社 | Nonaqueous electrolyte secondary battery |
-
2011
- 2011-02-04 US US13/020,854 patent/US20120202121A1/en not_active Abandoned
-
2012
- 2012-02-03 CN CN201280007668.8A patent/CN103733412A/en active Pending
- 2012-02-03 KR KR1020137023189A patent/KR20140025343A/en not_active Application Discontinuation
- 2012-02-03 JP JP2013552675A patent/JP2014516454A/en active Pending
- 2012-02-03 WO PCT/US2012/023774 patent/WO2012106598A2/en active Application Filing
- 2012-02-03 DE DE112012000670T patent/DE112012000670T5/en not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070015048A1 (en) * | 2005-07-13 | 2007-01-18 | Hochun Lee | Lithium secondary battery containing capsule for controlled-release of additives |
US20090092902A1 (en) * | 2005-07-29 | 2009-04-09 | Ali Abouimrane | Plastic crystal electrolyte for lithium batteries |
US20100119951A1 (en) * | 2007-05-11 | 2010-05-13 | Ali Abouimrane | Plastic Crystal Electrolyte with a Broad Potential Window |
US20090068562A1 (en) * | 2007-09-07 | 2009-03-12 | Kyoung-Han Yew | Rechargeable lithium battery |
US20100015521A1 (en) * | 2008-07-07 | 2010-01-21 | Jinhee Kim | Rechargeable battery and associated methods |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015083841A1 (en) * | 2013-12-03 | 2015-06-11 | University Of Massachusetts Amherst | Electrical insulation layer and battery device |
JP2017504932A (en) * | 2013-12-03 | 2017-02-09 | ユニバーシティー オブ マサチューセッツUniversity of Massachusetts | Electrical insulation layer and battery device |
US9853269B2 (en) | 2013-12-03 | 2017-12-26 | Sekisui Chemical Co., Ltd. | Electrical insulation layer and battery device |
Also Published As
Publication number | Publication date |
---|---|
KR20140025343A (en) | 2014-03-04 |
US20120202121A1 (en) | 2012-08-09 |
DE112012000670T5 (en) | 2013-10-31 |
JP2014516454A (en) | 2014-07-10 |
CN103733412A (en) | 2014-04-16 |
WO2012106598A3 (en) | 2014-03-20 |
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